Treating hydrocarbons



Patented June 23, 1942 V I "r OFFICE TREATING HYDROCARBONS August Y. Mottlau, Elizabeth, N. J., assignor to Standard Oil Development Company, a corporation of Delaware No Drawing. Application April 29, 1938, Serial No. 205,000

11 Claims.

The present invention relates to an improved process for removing sulfur compounds from mineral oils. It is particularly concerned with the process of removing organically combined sulfur compounds from mineral oils, as for example, from petroleum hydrocarbons, with solvents of the class of aliphatic amino alcohols.

It is known in the art to remove sulfur compounds from petroleum oils by means of various solvents. It is also known to scrub gaseous mixtures with solvents, as for example, diaminopropanol, diamino diethyl ether and the like in order to remove the acidic gases, as for example, hydrogen sulfide and carbon dioxide from the same. However, I have now found that substances of the class of aliphatic amino alcohols, particularly the diaminopropanols, are desirable and improved solvents for the process of removing mercaptan sulfur from liquid hydrocarbons.

Suitable solvents of the present invention are selected from the class of aliphatic amino alcohols. The preferred amino alcohols are those containing from 3 to 6 carbon atoms in the molecule. Especially desirable solvents for the present invention are the amino propanols containing two amino groups and a primary hydroxy group. However, other diaminopropanols, as for example, 1-3-diaminopropanol-2, 1-3-diamino- 2-methyl propanol-2 and 1-3-diamino-2-ethyl propanol-2, may also be used as well as aliphatic amino butanols and the like.

The process of the present invention of removing organic sulfur compounds from liquid mineral oils by means of solvents of the class of aliphatic amino alcohols may be carried out in any desirable manner. The process may be a countercurrent continuous treatment carried out in a tower containing suitable distributing and contacting means. The process may also be carried out in a. single stage or in a multi-batch treatment in which the petroleum oil and the aliphatic amino alcohol are intimately mixed in any desirable manner.

The temperature and pressure of treatment may be varied over a wide range, depending upon the type of stock being desulfurized and depending also upon the particular organic sulfur compounds being removed. In general it is preferred to use atmospheric pressure and a temperature in the range from 60 to 85 F.

These aliphatic amino alcohol organic sulfur solvents may be used in order to extract or reduce the mercaptan sulfur content in any mineral oil. They are, however, particularly effective in reducing the mercaptan sulfur content of a pretroleum mineral oil and thus may be readily and economically applied in the refining of petroleum hydrocarbons, as for example, naphtha, kerosene, Varsol, gas oil and the like.

The solvents of the present invention are particularly desirable for removing organic sulfur compounds from petroleum oils boiling in the range from 100 to 700 F. and especially from petroleum oils boiling in the range from 200 to 450 F.

The solvents of the present invention may be used in any manner desirable. It is, however, preferred to use an aqueous solution. The concentration will vary with the particular solvent being used, the stock being treated and type of organic sulfur compounds which are being removed. For example, in the. treatment of a cracked or virgin naphtha with diaminopropanol, it is preferred to use a concentration of diaminopropanol in the range from 40 to The volume of the organic sulfur solvent used to treat a fixed volume of the oil being desulfurized will also vary, depending upon the character of the oil, the particular solvent being used and the character of the organic sulfur compounds being removed, as well as upon the concentration of the solvent in the aqueous solution and temperature of treatment. In general, it is preferred to use from one-half to one volume of aqueous solvent per volume of oil being desulfurized.

In order to more fully illustrate the invention, the following examples are given and are not to be construed as limiting the scope of the invention in any manner whatsoever.

EXAMPLE I -An East Texas virgin naphtha of about the following specifications:

Table 1 Gravity A. P. I 62 Reid vapor pressure pounds 7.0 Initial boiling point Engler F 110 Per cent at 158 Engler 12.5 Final Engler 400 and containing 0.024% of sulfur was treated with an equal volume of an aqueous 40% solution of l-3-diaminopropanol-l at a temperature of about F. After a single batch treatment the sulfur content on the treated naphtha was 0.016%. The data may be summarized as follows;

Table 2 Table 7 Per cent Initial sulfur content of naphtha 0.024 100 Nommeb Final sulfur content of naphtha 0.016 67 ggg; gff tgf captan 355;. Sulfur reduction 0.008 33 5 Sulfur EXAMPLE 2 Initial sulfur content A West Texas cracked naphtha of about the S3i ohtmr M95 M80 M15 100 following specifications: f t 0-444 ur reduction of Table 3 10 naphtha 0.051 10.4 1333 2.255;'glisnllliililllfinin 158 Tnn nnnvn nnvnnnnn n nnn n n nnnnnn by Initial boiling point Engler 10 any theory any m 0f p l but y Per cent at Engler 25 by the following c1a1ms in which it is desired to Final Engler 400 clailm1 all novelty insofar as the prior art permits.

0 aim: and containing Of sulfur Was treated in L Proces for removing organic sulfur comthe manner described in Example 1 and the repounds of the mercaptan t from a mineral $111158 ay b s a e a f oil boiling in the range between 100 and 700 F. Table 4 comprising treating the same at atmospheric Per cent pressure and at a temperature in the range from Initial sulfur content of naphtha 0.209 100 60 with an aqueous solution of an Final sulfur content of naphtha 0.190 91 Phatlc ammonlcohol; S lfu reduction u 9 2. Process in accordance with claim 1 which said aliphatic amino alcohol contains from 3 to EXAMPLE 3 6 carbon atoms in the molecule. A gasoline having about th following Speci- 3. Process in accordance with claim 1 in which fications; said aliphatic amino alcohol is diaminopropanol. Table 5 Q 4. Process in accordance with claim 1 which said aliphatic amino alcohol is a diamino- Initial boiling point Engler 110 propanol containing a primary hydroxy group. Per cent off at 203 60 5. Process for removing organic sulfur com- Final boiling point 320 pounds of the mercaptan type from a petroleum oil boiling in the range from about 100 to 700 F. and containing a total sulfur content of 0.495%, comprising treating the Same at atmospheric of which 0.480% was mercaptan sulfur and 0.015% was non-mercaptan sulfur, .was treated in the following manner. The naphtha was extracted successfully five times with 30% by volume of an aqueous solution containing 60% diaminopropanol. The naphtha after these extractions was then washed in three successive treats with 30% by volume of pure water. The sulfur content of the treated naphtha was then determined and the results may be summarized as follows:

Table 6 Total Mercaptan ii gg Per cent sulfur sulfur fi total Initial sulfur content ofnaphtha 0.495 0.480 0.015 100 Sulfur content of treated naphtha 0.165 31.3 Sulfur reduction of naphtha 0.330 08.7

EXAMPLE 4 In order to determine the effect of water alone, the above described naphtha was treated with 8 successive treats of water using 30% of water per Volume of naphtha per treat. The results of this treatment may be summarized as followsz.

pressure and at a temperature in the range from 60 to F. with an aqueous solution of an aliphatic amino alcohol containing the latter in a concentration of 40 to 60%.

6. Process in accordance with claim 5 in which said aliphatic amino alcohol contains from 3 to 6 carbon atoms in the molecule.

'7. Process in accordance with claim 5 in which said aliphatic amino alcohol is diaminopropanol.

8. Process in accordance with claim 5 in which said aliphatic amino alcohol is 1-3-diaminopropanol-l.

9. Process of removing organic sulfur compounds of the mercaptan type from a petroleum oil boiling in the range from 200 to 450 F.

comprising treating the same with an equal volume of an aqueous solution of diaminopropanol having a concentration of 40 to 60% diaminopropanol.

10. Process for removing organic sulfur compounds of the mercaptan type from mineral oils boiling in the range between about F. and 700 F. comprising treating the same in the liquid phase with an aqueous solution of an aliphatic amino alcohol...

11'. Process in accordance with claim 10 in which said aliphatic amino alcohol is diamino propanol.

AUGUST Y..MOTTLAU. 

